CN115894069B - Porous silicon carbide high-temperature heat-insulating tile and preparation method thereof - Google Patents
Porous silicon carbide high-temperature heat-insulating tile and preparation method thereof Download PDFInfo
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Abstract
Porous silicon carbide high-temperature heat-insulating tile and preparation method thereof, 1) PVG powder and SiC (rGO) are mixed p Ball milling and mixing ceramic filler powder, drying and grinding, adding graphite powder pore-forming agent, and uniformly mixing to obtain SiC (rGO) p PVG/C mixed powder; 2) SiC (rGO) p Pouring the PVG/C mixed powder into a mould, pressing for molding, demoulding, putting into a crucible filled with graphite paper, and carrying out high-temperature re-cracking in a tube furnace under the protection of inert atmosphere to obtain a SiC (rGO)/C ceramic sheet; 3) Placing the SiC (rGO)/C ceramic sheet in an air furnace to remove carbon and form holes to obtain SiC (rGO) x A porous ceramic, wherein x represents the mass fraction of the additive pore-forming agent; 4) SiC (rGO) x Porous ceramics impregnated with silicon solutionAnd taking out the glue and performing high-temperature pyrolysis under the protection of inert atmosphere to obtain the repaired porous silicon carbide high-temperature heat-insulating tile material.
Description
Technical Field
The invention relates to the field of ceramic materials, in particular to a porous silicon carbide high-temperature heat-insulating tile and a preparation method thereof.
Background
Reusable launch vehicles, planetary probes and hypersonic aircraft are subjected to severe aerodynamic heating environments with medium-low heat flow and long heating time, and the heat will peak when rising at high speed and returning to the atmosphere. In order to ensure that the temperature inside the aircraft remains normal, development of a high-reliability heat protection system is widely focused, wherein the heat insulation performance and stability of a heat protection material become important factors for restricting development of a novel aerospace aircraft. The thermal protection material must possess a high resistance to extreme environmental conditions in order to meet the thermal protection system temperature, durability and reliability requirements of the aircraft. The heat insulation material with light weight, high strength, low heat conduction, high temperature resistance, oxidation resistance and thermal shock resistance is usually of a porous structure, is convenient to install and high in stability, and provides a new scheme for the development of a heat protection system.
Aiming at the problem of large-area heat protection, high-temperature heat-insulating tile materials such as ceramic fiber heat-insulating materials, aerogel heat-insulating materials and porous ceramic heat-insulating materials exist at present. The Chinese patent ZL 20171063144.2 discloses a preparation method of mullite fiber heat-insulating tiles, which takes mullite fibers as raw materials and prepares the mullite fiber high-temperature heat-insulating tiles through operations such as shearing, mixing, stirring, suction filtration, drying, glue discharging, sintering and the like. Chinese patent CN 113980343A discloses an ablation-resistant modified phenolic aerogel thermal protection material and a preparation method thereof, adopts boron compounds to carry out inorganic modification on siloxane phenolic resin, and then carries out the steps of dissolution, crosslinking, heating curing, drying and the like to prepare the ablation-resistant modified phenolic aerogel with high compressive strength and low thermal conductivity, and is expected to be applied to the field of external thermal protection of high-speed aircrafts. However, the high-temperature heat-insulating tile materials usually realize low heat conduction by sacrificing mechanical properties, cannot achieve light-weight high-strength integration, have the problems of poor heat shock resistance, complex process, difficulty in large-scale production and the like, and limit further application.
The silicon carbide (SiC) porous ceramic is used as a typical porous ceramic heat insulation material, has the advantages of low density, low heat conduction, wear resistance, high specific strength, strong impact resistance, good high-temperature stability and the like, can effectively prevent aerospace devices from being severely damaged by pneumatic heating and strong surface pressure, and meets the application requirements of aircrafts under complex severe environments. Currently, the preparation methods of SiC ceramics include reaction sintering, hot press sintering, pressureless sintering, spark plasma sintering, polymer precursor methods, and the like. Chinese patent CN112279648A discloses a method for preparing pressureless sintered high toughness SiC, in which graphene is added, and the fracture toughness is about 20% higher than that of ordinary pressureless sintering. Chinese patent CN 111484019a discloses a method for preparing high purity SiC powder for single crystal growth, which comprises mixing high purity graphite powder, high purity Si powder and polytetrafluoroethylene powder, and repeatedly injecting high purity H 2 And the high-purity alpha-SiC powder is obtained by conversion synthesis after the treatments of vacuumizing, heating, temperature rising and the like, and is suitable for the growth of high-purity semi-insulating SiC single crystals. Chinese patent CN 113735591a discloses a preparation method for preparing nitrogen doped conductive SiC ceramic by spark plasma sintering, which uses yttrium oxide, aluminum oxide and SiC powder as raw materials, and obtains SiC ceramic with good mechanical properties and low resistivity by ball milling, drying, tabletting, high temperature sintering and other processes. Chinese patent CN 113061036A discloses a complex structure carbon fiber/SiC whisker reinforced SiC composite material and a preparation method thereof, wherein silicon carbide, chopped carbon fiber and thermoplastic phenolic resin are used as raw materials, and the composite material is prepared by the operations of 3D printing forming, infiltration, twice heat treatment, siliconizing process and the like to obtain the composite material with excellent mechanical propertyThe carbon fiber-SiC whisker reinforced SiC composite material is suitable for hypersonic aircraft heat protection systems. However, the above method usually requires the introduction of sintering aids, and has certain limitations in terms of mechanical properties, corrosion resistance, shape diversity, production cost and the like of products.
The precursor method does not need to add sintering auxiliary agent, avoids the influence of impurities on the thermal protection performance of the material, can regulate and control the microstructure and performance of the ceramic by grafting and modifying polymer precursor molecules, improves the thermal mechanical performance and stability of the ceramic, reduces the sintering temperature, and is easy to manufacture samples with complex shapes. The SiC polymer precursor porous ceramic has excellent high temperature resistance, oxidation resistance and ablation resistance, and is expected to meet the requirement of high-speed aircrafts on light high-strength heat protection materials.
Chinese patent CN 114195519a discloses a precursor-converted silicon carbide ceramic and a preparation technique thereof, and uses SiC ceramic powder and SiC precursor as raw materials to perform a series of operations such as ball milling, heat preservation, sintering, etc., so as to prepare the SiC ceramic. Chinese patent ZL 200510032364.9 discloses a method for preparing carbon fiber/silicon carbide high temperature resistant anti-scouring heat protection plate by precursor method, wherein polysiloxane precursor solution is immersed on carbon fiber fabric and then high temperature cracking is carried out to obtain the heat protection plate. The traditional precursor ceramic is mostly fiber and film because a large amount of micromolecular gas escapes in the high-temperature cracking process, so that the sample generates air hole defects and even cracks, the structural integrity is damaged, and the sample is contracted, thus the preparation of bulk ceramic is difficult to realize, and great inconvenience is brought to subsequent application.
Chinese patent ZL 201711494377.7 describes a graphene/silicon carbide nano composite structure monolithic ceramic and a preparation method thereof, solves the problem of difficult formation of silicon carbide precursor ceramic, effectively improves the physical properties of the silicon carbide monolithic ceramic, reduces the production cost, and is beneficial to large-scale production and wide application. The Chinese patent ZL 201910826944.7 discloses a preparation method of bulk silicon carbide polymer precursor ceramic and blending and re-cracking, and the obtained ceramic has the advantages of higher yield, lower linear shrinkage, good hardness and fracture toughness, uniform and compact microstructure, fewer pores, microcracks and interfaces, strong practicability and reliability, and can meet the ceramic preparation requirements of complex structural design. Although these SiC precursor ceramics have a certain porosity, they have a high carbon content, poor oxidation resistance, weak heat insulating properties, and high density, and are not suitable as thermal protective materials. Because the heat conductivity of air is far lower than that of ceramic material, the SiC precursor ceramic heat-insulating tile material with porous structure can effectively prevent heat from diffusing inwards. The simplest and most economical pore-forming method aiming at the one-step forming of the precursor ceramic is a pore-forming agent method at present, has the advantages of low cost, easy regulation and control and strong universality, and the widely used polymer pore-forming agent finishes the change of vaporization pore-forming before the precursor is subjected to ceramic conversion, is not beneficial to the maintenance of the shape of a ceramic skeleton and influences the mechanical property of the porous material.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide the porous silicon carbide high-temperature heat-insulating tile which has low density, low heat conductivity and high mechanical strength and can be manufactured into complex shapes.
It is another object of the present invention to provide a simple and economical method for preparing the porous silicon carbide high temperature insulating tile described above, suitable for industrial production.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the porous silicon carbide high-temperature heat-insulating tile comprises the following steps:
1) PVG powder and SiC (rGO) p Ball-milling and mixing ceramic filler powder, drying and grinding, and finally adding a graphite powder pore-forming agent, and uniformly mixing to obtain SiC (rGO) p PVG/C mixed powder;
2) SiC (rGO) as described in step 1) p Pouring the PVG/C mixed powder into a mould, pressing for molding, demoulding, putting into a crucible filled with graphite paper, and carrying out high-temperature re-cracking in a tube furnace under the protection of inert atmosphere to obtain a SiC (rGO)/C ceramic sheet;
3) Placing the SiC (rGO)/C ceramic sheet obtained in the step 2) into an air furnace to remove carbon and form holes to obtain a porous silicon carbide high-temperature heat-insulating tile material, namely SiC (rGO) x Porous ceramics, wherein x represents the raw material systemAdding the mass fraction of the pore-forming agent;
4) Obtaining SiC (rGO) from the step 3) x Soaking porous ceramic in silica sol solution, and then taking out for high-temperature pyrolysis under the protection of inert atmosphere to obtain the repaired porous silicon carbide high-temperature heat-insulating tile material, siC (rGO) for short x /SiO 2 The porous ceramic, wherein x represents the mass fraction of the pore-forming agent added in the raw material system.
In the step 1), the precursor PVG powder can be self-made PVG powder, and the preparation method refers to the prior patent ZL 202010722118.0 of the applicant; said SiC (rGO) p The ceramic filler powder can be obtained by high-temperature pyrolysis of precursor PVG, and the preparation method can be referred to the prior patent ZL 202010722118.0 of the applicant; the particle size of the graphite powder is 800-3000 meshes.
In the step 1), the ball milling adopts a positive and negative transfer mode, the rotating direction is changed every 0.5-2 h, and the ball milling time is 8-10 h.
In step 1), siC (rGO) is added according to the mass ratio p 36 to 54 percent of filler powder, 24 to 36 percent of PVG powder, 10 to 40 percent of graphite powder.
In the step 2), the die adopts a stainless steel die, the pressure of the compression molding is 90-110 MPa, and the pressure maintaining time is 15-20 s.
In the step 2), in the Gao Wenzai pyrolysis, argon is adopted as inert gas, and the flow rate is 50-80 mL-min -1 The temperature is 1200-1400 ℃, the temperature rising rate is 3-5 ℃ min -1 The heat preservation time is 25-40 min.
In the step 3), the air furnace is a high-temperature box type furnace, and the temperature rising rate is 6-8 ℃ and min -1 The oxidation temperature is 600-800 ℃, and the heat preservation time is 1-5 h.
In step 4), the silica sol is mSiO 2 ·nH 2 O solution with concentration of 10-30%; the dipping time is 12-48 h, the high-temperature cracking temperature is 1100-1400 ℃, and the inert atmosphere is argon.
The step 4) can be repeated 1 to 2 times.
The porous silicon carbide high-temperature heat insulation tile prepared by the preparation method of the porous silicon carbide high-temperature heat insulation tileThermal tiles with polymer precursors polycarbosilane-vinyltrioxysilane-graphene oxide (PVG), siC (rGO) p The ceramic filler, the graphite powder pore-forming agent and the silica sol are used as raw materials, and the ceramic filler, the graphite powder pore-forming agent and the silica sol are prepared by adopting the processes of ball milling, blending and cracking, compression molding, high-temperature cracking, oxidative decarbonization, impregnation of an antioxidant coating, repairing of macropores and the like. The precursor method, the blending and re-cracking technology and the pore-forming agent method are combined, and on the premise of ensuring excellent mechanical properties of the skeleton, high-temperature pore forming is adopted, so that the porous ceramic skeleton shape is kept, meanwhile, redundant free carbon weakening the mechanical properties in the ceramic skeleton is removed, a dual pore structure is formed, and the light high-strength and heat insulation integration of the porous silicon carbide high-temperature heat insulation tile material is realized.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) The porous silicon carbide high-temperature heat-insulating tile material prepared by the invention has a ceramic skeleton microstructure that beta-SiC crystal grains are dispersed and distributed in SiOxCy/C free In the matrix, there is a small amount of SiC (rGO) p Ball milling in the process SiO produced 2 The microcrystals are distributed in the porous ceramic material, so that the porous ceramic material has good forming performance and mechanical strength, simultaneously the pore-forming agent method effectively reduces the heat conductivity of a sample, has the advantages of high ceramic yield, low linear shrinkage, low density, low heat conductivity, high temperature resistance, strong oxidation resistance and the like, and realizes the integration of heat prevention and heat insulation.
(2) The porous silicon carbide high-temperature heat-insulating tile material prepared by the invention has a double pore structure, PVG powder and SiC (rGO) p The ceramic filler powder is subjected to blending and pyrolysis to form beta-SiC/SiOxCy/C with integrated structure free (rGO) matrix skeleton, graphite pore-forming agent forms ellipsoidal macropores with uniform distribution in the oxidation decarbonization pore-forming process, and part C in the skeleton free The (rGO) is oxidized along with the pore-forming agent to form uniformly distributed micropores, so as to play a role in pinning, relieve thermal stress and relax internal stress, and facilitate the improvement of mechanical properties of materials.
(3) The invention adopts the high temperature resistant graphite pore-forming agent to regenerate macropores after ceramic transformation of the precursor, which is beneficial to the maintenance of the shape of the ceramic skeleton so as to improve the mechanical property of the porous material; at the same time, the carbon in the ceramic skeleton is removed to make micropores, and no impurity is introduced. The porous silicon carbide high-temperature heat-insulating tile material has the advantages that the mechanical strength is improved while the low heat conductivity is kept, the process is simple, the one-step molding is realized, an auxiliary agent is not needed, and the influence of impurities on the heat protection performance of the material is avoided.
(4) The method has simple and economic process, can regulate and control the properties of ceramic strength, porosity and the like by adjusting the proportion of pore-forming agents, removing carbon by oxidation and impregnating and repairing processes, and is beneficial to realizing industrial production.
Drawings
FIG. 1 shows SiC (rGO) prepared in examples 1 to 3 of the present invention 10 、SiC(rGO) 20 /SiO 2 、SiC(rGO) 40 /d-SiO 2 X-ray diffraction (XRD) patterns of (a).
FIG. 2 shows SiC (rGO) prepared in example 3 of the present invention 20 、SiC(rGO) 40 、SiC(rGO) 40 /SiO 2 、SiC(rGO) 40 /d-SiO 2 Surface of (2) Scanning Electron Microscopic (SEM) images; in FIG. 2, (a) (d) is SiC (rGO) 20 (b) (e) is SiC (rGO) 40 (c) SiC (rGO) 40 /SiO 2 (f) SiC (rGO) 40 /d-SiO 2 。
FIG. 3 shows SiC (rGO) prepared in example 3 of the present invention 40 Transmission Electron Microscope (TEM) images of (a); in fig. 3, the left plot corresponds to a low-power transmission electron microscope image TEM and the right plot corresponds to a high-resolution transmission electron microscope image HRTEM.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
1. Placing precursor PVG powder into a tube furnace, and performing high-temperature pyrolysis at 1300 ℃ in an argon atmosphere, wherein the argon flow rate is 60 mL.min -1 The temperature rising rate is 4 ℃ min -1 The heat preservation time is 30min, and SiC (rGO) is obtained after cooling along with the furnace p Ceramic powder.
2. PVG powder and SiC (rGO) p The ceramic powder is ball-milled and mixed by adopting a planetary ball mill, wherein PVG powder and SiC (rGO) are mixed by adopting the planetary ball mill p The mass ratio of the ceramic powder to the grinding balls is 4:6:40, the ball milling medium is absolute ethyl alcohol, the ball milling time is 9 hours, and the rotating direction is changed every 1 hour by adopting a forward and reverse conversion mode. After ball milling, the raw materials are put into a baking oven to be dried and ground, thus obtaining SiC (rGO) with uniform particles p PVG mixture.
3. Mixing 10wt.% graphite powder (particle size 2000 mesh) with SiC (rGO) p Uniformly mixing the PVG mixture to obtain SiC (rGO) p PVG/C mixed powder. Respectively pouring 1g of mixed powder into a round stainless steel die, maintaining the pressure of an oil press at 100MPa for 20s for compression molding, and demolding to obtain SiC (rGO) p PVG/C and (3) ceramic green body.
4. Placing the ceramic green compact in a crucible filled with graphite paper, placing in a tubular furnace, and performing high-temperature pyrolysis again at 1300 ℃ under argon atmosphere, wherein the flow rate of argon is 60 mL.min -1 The temperature rising rate is 4 ℃ min -1 The heat preservation time is 30min, and the SiC (rGO)/C ceramic plate is obtained after cooling along with the furnace.
5. Placing the SiC (rGO)/C ceramic sheet in a high-temperature box furnace for oxidation decarbonization, and heating at a temperature rate of 7 ℃ for min -1 The porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) is obtained after the oxidation temperature is 700 ℃ and the heat preservation time is 3 hours and then the porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) is cooled along with the furnace 10 Porous ceramics.
6. SiC (rGO) to be obtained 10 Porous ceramics are immersed in mSiO with concentration of 20% at normal pressure 2 ·nH 2 Taking out the porous silicon carbide high-temperature heat-insulating tile material after 24h in O solution, and carrying out high-temperature pyrolysis at 1200 ℃ under argon atmosphere to obtain porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) 10 /SiO 2 Porous ceramics.
7. SiC (rGO) to be obtained 10 /SiO 2 Porous ceramics are immersed in mSiO again at normal pressure 2 ·nH 2 Taking out the porous silicon carbide high-temperature heat-insulating tile material after 24h in O solution, and carrying out high-temperature pyrolysis at 1200 ℃ under argon atmosphere to obtain porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) 10 /d-SiO 2 Porous ceramics.
Example 2
1. Placing precursor PVG powder into a tube furnace, and performing high-temperature pyrolysis at 1300 ℃ in an argon atmosphere, wherein the argon flow rate is 60 mL.min -1 The temperature rising rate is 4 ℃ min -1 The heat preservation time is 30min, and SiC (rGO) is obtained after cooling along with the furnace p Ceramic powder.
2. PVG powder and SiC (rGO) p The ceramic powder is ball-milled and mixed by adopting a planetary ball mill, wherein PVG powder and SiC (rGO) are mixed by adopting the planetary ball mill p The mass ratio of the ceramic powder to the grinding balls is 4:6:40, the ball milling medium is absolute ethyl alcohol, the ball milling time is 9 hours, and the rotating direction is changed every 1 hour by adopting a forward and reverse conversion mode. After ball milling, the raw materials are put into a baking oven to be dried and ground, thus obtaining SiC (rGO) with uniform particles p PVG mixture.
3. 20wt.% of graphite powder (particle size 2000 mesh) and SiC (rGO) are mixed together p Uniformly mixing the PVG mixture to obtain SiC (rGO) p PVG/C mixed powder. Respectively pouring 1g of mixed powder into a round stainless steel die, maintaining the pressure of an oil press at 100MPa for 20s for compression molding, and demolding to obtain SiC (rGO) p PVG/C ceramic green body.
4. Placing the ceramic green compact in a crucible filled with graphite paper, placing in a tubular furnace, and performing high-temperature pyrolysis again at 1300 ℃ under argon atmosphere, wherein the flow rate of argon is 60 mL.min -1 The temperature rising rate is 4 ℃ min -1 The heat preservation time is 30min, and the SiC (rGO)/C ceramic plate is obtained after cooling along with the furnace.
5. Placing the SiC (rGO)/C ceramic sheet in a high-temperature box furnace for oxidation decarbonization, and heating at a temperature rate of 7 ℃ for min -1 The porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) is obtained after the oxidation temperature is 700 ℃ and the heat preservation time is 3 hours and then the porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) is cooled along with the furnace 20 Porous ceramics.
6. SiC (rGO) to be obtained 20 Porous ceramic atmospheric impregnation at a concentration of 20% mSiO 2 ·nH 2 Taking out after 24h in O solution, carrying out high-temperature pyrolysis at 1200 ℃ in argon atmosphere, obtaining porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) 20 /SiO 2 Porous ceramics.
7. SiC (rGO) to be obtained 20 /SiO 2 Porous ceramics are immersed in mSiO again at normal pressure 2 ·nH 2 Taking out the porous silicon carbide high-temperature heat-insulating tile material after 24h in O solution, and carrying out high-temperature pyrolysis at 1200 ℃ under argon atmosphere to obtain porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) 20 /d-SiO 2 Porous ceramics.
Example 3
1. Placing precursor PVG powder into a tube furnace, and performing high-temperature pyrolysis at 1300 ℃ in an argon atmosphere, wherein the argon flow rate is 60 mL.min -1 The temperature rising rate is 4 ℃ min -1 The heat preservation time is 30min, and SiC (rGO) is obtained after cooling along with the furnace p Ceramic powder.
2. PVG powder and SiC (rGO) p The ceramic powder is ball-milled and mixed by adopting a planetary ball mill, wherein PVG powder and SiC (rGO) are mixed by adopting the planetary ball mill p The mass ratio of the ceramic powder to the grinding balls is 4:6:40, the ball milling medium is absolute ethyl alcohol, the ball milling time is 9 hours, and the rotating direction is changed every 1 hour by adopting a forward and reverse conversion mode. After ball milling, the raw materials are put into a baking oven to be dried and ground, thus obtaining SiC (rGO) with uniform particles p PVG mixture.
3. Mixing 40wt.% graphite powder (particle size 2000 mesh) with SiC (rGO) p Uniformly mixing the PVG mixture to obtain SiC (rGO) p PVG/C mixed powder. Respectively pouring 1g of mixed powder into a round stainless steel die, maintaining the pressure of an oil press at 100MPa for 20s for compression molding, and demolding to obtain SiC (rGO) p PVG/C ceramic green body.
4. Placing the ceramic green compact in a crucible filled with graphite paper, placing in a tubular furnace, and performing high-temperature pyrolysis again at 1300 ℃ under argon atmosphere, wherein the flow rate of argon is 60 mL.min -1 The temperature rising rate is 4 ℃ min -1 The heat preservation time is 30min, and the SiC (rGO)/C ceramic plate is obtained after cooling along with the furnace.
5. Placing the SiC (rGO)/C ceramic sheet in a high-temperature box furnace for oxidation decarbonization, and heating at a temperature rate of 7 ℃ for min -1 The porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) is obtained after the oxidation temperature is 700 ℃ and the heat preservation time is 3 hours and then the porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) is cooled along with the furnace 40 Porous ceramics.
6. SiC (rGO) to be obtained 40 Porous ceramics are immersed in mSiO with concentration of 20% at normal pressure 2 ·nH 2 Taking out the porous silicon carbide high-temperature heat-insulating tile material after 24h in O solution, and carrying out high-temperature pyrolysis at 1200 ℃ under argon atmosphere to obtain porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) 40 /SiO 2 Porous ceramics.
7. SiC (rGO) to be obtained 40 /SiO 2 Porous ceramics are immersed in mSiO again at normal pressure 2 ·nH 2 Taking out the porous silicon carbide high-temperature heat-insulating tile material after 24h in O solution, and carrying out high-temperature pyrolysis at 1200 ℃ under argon atmosphere to obtain porous silicon carbide high-temperature heat-insulating tile material SiC (rGO) 40 /d-SiO 2 Porous ceramics.
The porous silicon carbide high-temperature heat-insulating tile material prepared by the invention has the following characteristics: low density, low thermal conductivity and high mechanical strength. The porous silicon carbide high-temperature heat-insulating tile material has wide peaks belonging to beta-SiC in an X-ray (XRD) diagram (figure 1), wherein 2 theta is about 35.7 degrees, 60.1 degrees and 71.8 degrees respectively, and the corresponding (111), (220) and (311) crystal faces indicate that the crystallinity of a sample is lower. At the same time, peaks at about 20.8 ° and 26.5 ° 2θ, corresponding to SiO 2 And (3) quartz crystal. SiO with the increase of the addition amount of the pore-forming agent and the times of the dipping repair process 2 The intensity ratio of the peak to the broad peak of beta-SiC is gradually increased, and the repairing effect is verified.
The surface of the SiC (rGO) porous polymer precursor ceramic high-temperature heat-insulating tile material has the following characteristics in a scanning electron microscope analysis chart (figure 2): the SiC (rGO) porous ceramic has a relatively flat surface, a compact ceramic skeleton and uniform pore distribution. As the number of silica sol impregnations increases, the number of surface pores of the sample gradually decreases and the surface of the sample tends to be smooth. The SiC (rGO) porous ceramic has obvious double pore structure (micropores in the ceramic framework and macropores among the frameworks), wherein the macropores among the frameworks are formed by oxidizing pore formers and are mostly round, and the micropores in the ceramic framework are part C in the framework free (rGO) together with pore-forming agent is oxidized.
The surface of the SiC (rGO) porous polymer precursor ceramic high-temperature heat-insulating tile material has the following characteristics in a transmission electron microscope analysis chart (figure 3): three bright concentric rings can be observed from the selected area electron diffraction pattern,the crystal faces (111), (220) and (311) corresponding to beta-SiC respectively show that the porous silicon carbide high-temperature heat-insulating tile material is a polycrystal with lower crystallinity and is mostly amorphous SiOxCy/C free Phase, high resolution transmission electron microscopy image HRTEM can observe that beta-SiC crystal grains are dispersed and distributed in SiOxCy/C free In the matrix, the compatibility of the two is good, and a small amount of unoxidized rGO can be observed.
Table 1 shows basic physical parameters (volume density and open pore volume fraction) of the porous silicon carbide high temperature heat insulation tile material hardness and thermal conductivity.
Watch (watch) 1
The above-described embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (10)
1. The preparation method of the porous silicon carbide high-temperature heat-insulating tile is characterized by comprising the following steps of:
1) PVG powder and SiC (rGO) p Ball-milling and mixing ceramic filler powder, drying and grinding, and finally adding a graphite powder pore-forming agent, and uniformly mixing to obtain SiC (rGO) p PVG/C mixed powder;
2) SiC (rGO) as described in step 1) p Pouring the PVG/C mixed powder into a mould, pressing for molding, demoulding, putting into a crucible filled with graphite paper, and carrying out high-temperature re-cracking in a tube furnace under the protection of inert atmosphere to obtain a SiC (rGO)/C ceramic sheet;
3) Placing the SiC (rGO)/C ceramic sheet obtained in the step 2) into an air furnace to remove carbon and form holes to obtain a porous silicon carbide high-temperature heat-insulating tile material, namely SiC (rGO) x Porous ceramic, whereinxRepresenting the mass fraction of the pore-forming agent added into the raw material system;
4) Obtaining SiC (rGO) from the step 3) x Soaking porous ceramic in silica sol solution, and then taking out for high-temperature pyrolysis under the protection of inert atmosphere to obtain the repaired porous silicon carbide high-temperature heat-insulating tile material, siC (rGO) for short x /SiO 2 Porous ceramic, whereinxRepresenting the mass fraction of the pore-forming agent added into the raw material system.
2. The method for preparing the porous silicon carbide high-temperature heat-insulating tile as claimed in claim 1, wherein the method comprises the following steps: in the step 1), the particle size of the graphite powder is 800-3000 meshes.
3. The method for preparing the porous silicon carbide high-temperature heat-insulating tile as claimed in claim 1, wherein the method comprises the following steps: in the step 1), the ball milling adopts a positive and negative transfer mode, the rotating direction is changed every 0.5-2 h, and the ball milling time is 8-10 h.
4. The method for preparing the porous silicon carbide high-temperature heat-insulating tile as claimed in claim 1, wherein the method comprises the following steps: in step 1), siC (rGO) is added according to the mass ratio p 36-54% of filler powder, 24-36% of PVG powder and 10-40% of graphite powder.
5. The method for preparing the porous silicon carbide high-temperature heat-insulating tile as claimed in claim 1, wherein the method comprises the following steps: in the step 2), the die adopts a stainless steel die, the pressure of compression molding is 90-110 MPa, and the pressure maintaining time is 15-20 s.
6. The method for preparing the porous silicon carbide high-temperature heat-insulating tile as claimed in claim 1, wherein the method comprises the following steps: in the step 2), in the Gao Wenzai pyrolysis, argon is adopted as inert gas, and the flow rate is 50-80 mL-min -1 The temperature is 1200-1400 ℃, the temperature rising rate is 3-5 ℃ min -1 The heat preservation time is 25-40 min.
7. The method for preparing the porous silicon carbide high-temperature heat-insulating tile as claimed in claim 1, wherein the method comprises the following steps: in the step 3), the air furnace isHigh-temperature box-type furnace with heating rate of 6-8 ℃ min -1 The oxidation temperature is 600-800 ℃, and the heat preservation time is 1-5 h.
8. The method for preparing the porous silicon carbide high-temperature heat-insulating tile as claimed in claim 1, wherein the method comprises the following steps: in step 4), the silica sol is mSiO 2 ·nH 2 The concentration of the O solution is 10% -30%; the soaking time is 12-48 h, the high-temperature cracking temperature is 1100-1400 ℃, and the inert atmosphere is argon.
9. The method for preparing the porous silicon carbide high-temperature heat-insulating tile as claimed in claim 1, wherein the method comprises the following steps: and 4) repeating the step 4) for 1-2 times.
10. The porous silicon carbide high-temperature heat-insulating tile prepared by the preparation method of the porous silicon carbide high-temperature heat-insulating tile according to any one of claims 1-9.
Priority Applications (1)
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